Diverting Hydrogenations with Wilkinson's Catalyst towards Highly Reactive Rhodium(I) Species

Jesus E. Perea-Buceta, Israel Fernández, Sami Heikkinen, Kirill Axenov, Alistair W.T. King, Teemu Niemi, Martin Nieger, Markku Leskelä, Timo Repo*

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

18 Citations (Scopus)

Abstract

The addition of Barton's base has a dramatic effect on the classic rhodium(III)-mediated hydrogenations promoted by Wilkinson′s catalyst. Following the initial oxidative addition, a barrierless reductive elimination of HCl from the traditional rhodium(III) intermediates instantly produces a rhodium(I) monohydride species, which is remarkably reactive in the hydrogenation of several internal alkynes and functionalized trisubstituted alkenes. The direct formation of this species is unprecedented upon addition of molecular hydrogen and its catalytic potential has been hitherto barely explored.

Original languageEnglish
Pages (from-to)14321-14325
Number of pages5
JournalAngewandte Chemie: International Edition
Volume54
Issue number48
DOIs
Publication statusPublished - 23 Nov 2015
MoE publication typeA1 Journal article-refereed

Keywords

  • density functional calculations
  • homogeneous hydrogenation
  • reaction mechanisms
  • rhodium(I)
  • Wilkinson's catalyst

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